US3210327A - Symmetrical diol alkyl esters of acrylic acids and polymers thereof - Google Patents
Symmetrical diol alkyl esters of acrylic acids and polymers thereof Download PDFInfo
- Publication number
- US3210327A US3210327A US196914A US19691462A US3210327A US 3210327 A US3210327 A US 3210327A US 196914 A US196914 A US 196914A US 19691462 A US19691462 A US 19691462A US 3210327 A US3210327 A US 3210327A
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- Prior art keywords
- polymerizable compound
- polymers
- formula
- homopolymer
- beta
- Prior art date
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- Expired - Lifetime
Links
- 229920000642 polymer Polymers 0.000 title description 17
- 150000001253 acrylic acids Chemical class 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 43
- 239000000178 monomer Substances 0.000 claims description 30
- 229920001577 copolymer Polymers 0.000 claims description 15
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 5
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 5
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- -1 diol compounds Chemical class 0.000 description 23
- 229920001519 homopolymer Polymers 0.000 description 22
- 238000000034 method Methods 0.000 description 19
- 150000002009 diols Chemical class 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229920001897 terpolymer Polymers 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 125000000532 dioxanyl group Chemical group 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SJRFBMBWOZJHGU-UHFFFAOYSA-N 1,4-dioxan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC1COCCO1 SJRFBMBWOZJHGU-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical compound CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- ZIDIOHIXUSAZJA-UHFFFAOYSA-N (2,2,5-trimethyl-1,3-dioxan-5-yl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1(C)COC(C)(C)OC1 ZIDIOHIXUSAZJA-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229920003270 Cymel® Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- FPODCVUTIPDRTE-UHFFFAOYSA-N bis(prop-2-enyl) hexanedioate Chemical compound C=CCOC(=O)CCCCC(=O)OCC=C FPODCVUTIPDRTE-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MPFUOCVWJGGDQN-UHFFFAOYSA-N butan-1-ol;1,2-xylene Chemical group CCCCO.CC1=CC=CC=C1C MPFUOCVWJGGDQN-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical compound CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical class O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000011953 free-radical catalyst Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229940047889 isobutyramide Drugs 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000003797 telogen phase Effects 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
Definitions
- This invention relates to novel diol compounds. More particularly, it relates to novel symmetrical diols consisting of 1,3-prtpane diols having a 2-acrylic ester substitucut.
- the compounds are represented by the following formula:
- R is a hydrogen or a lower alkyl radical (preferably hydrogen or methyl), R is a lower alkyl radical having one to four carbon atoms or hydrogen, and n represents an integer from one to four, inclusive.
- the symmetrical diols of this invention are generally relatively high boiling liquids. They are water-soluble and are in general soluble in polar solvents such as lower alkanols, e.g., methanol and ethanol, and in acetone, dioxane, ethyl acetate, and the like.
- the compounds of this invention can be homopolymerized or copolymerized with another polymerizable ethylenically unsaturated compound to form interpolymers.
- the polymers thereby provided have the interesting characteristic of being in most instances soluble in solvent combinations of water and water-miscible polar solvent such as acetone, ethanol, and the like. However, they on the other hand are not generally readily solubilized in Water alone.
- Suitable dicarboxylic acids for the ester formations include both aryl and aliphatic dicarboxylic acids illustrative of which are succinic, adipic, ophthalic, terephthalic, sebacic, 1,4-naphthalene-dicarboxylic, azelaic, glutaric, 3-ethylsebacic, and the like carboxylic acids.
- corresponding acid halides or anhydrides can be employed as the dicarboxylic acid agent. Relative proportions of the diols and dicarboxylic acids will be selected to insure polyester formation.
- polyesters can be readily cured to form thermoset polymers conventionally by heating an admixture of the polymer and a catalytic amount of a free radical initiator such as a suitable peroxide, e.g., t-butyl perbenzoate.
- a free radical initiator such as a suitable peroxide, e.g., t-butyl perbenzoate.
- a quantity of a monomer can be added in preparation of the thermoset polymers to promote the linking of a double bonds of the acrylic substituents.
- Such monomers having unsaturation as styrene, triallyl isocyanurate, and the like can be employed for this purpose.
- polyurethanes can be provided by reacting the diol with an organic diisocyanate such as toluene diisocyanate and hexamethylene diisocyanate, and the like.
- organic diisocyanate such as toluene diisocyanate and hexamethylene diisocyanate, and the like.
- the diols of this invention can readily be prepared as 3,210,327 Patented Oct. 5, 1965 ice by a mild aqueous acid hydrolysis of S-alkylene-m-dioxanyl acrylic esters such as disclosed in US. patent application filed concurrently herewith, Serial No. 196,916, by David Rankin et al.
- the following equation illustrates the hydrolysis procedure:
- R, R and n have the definitions set forth above.
- the carbon atom occupying position 2 in the dioxanyl ring can have any substituents to fulfill the valence requirements so long as the substituents do not prevent the necessary hydrolysis.
- the substituents are desirably both lower alkyl, suitably methyl, because of the relative ease by which such ketals hydrolyse to the desired compounds and the economy of such intermediates.
- substituents can alternatively be ethyl, propyl, phenyl, or the like.
- the hydrolysis is carried on by adding a suitable amount of the acrylic dioxanyl ester to an inert aqueous reaction solvent.
- Water is a satisfactory reaction solvent.
- the mixture is acidified'by adding a suitable acid. Mineral acids such as hydrochloric and sulfuric acid are satisfactory for this purpose.
- the pH of the reaction mixture is advisably lowered to about pH 5 or below, preferably to a pH in the range of about pH 2 to about pH 4.
- the reaction temperature can be room temperature but presently is preferred to be slightly above to provide a more eflicient and rapid hydrolysis, e.g., a temperature in the range of about 30 C. to about 60 C. is ordinarily satisfactory.
- reaction time of from about one-half to about ten hours is ordinarily sufficient, depending on conditions and the intermediate employed.
- the reaction mixture is neutralized, is filtered, and the desired product is isolated as by extraction. Chloroform has been found to be a satisfactory extractant for aqueous reaction mixtures.
- ester exchange reactions by which the intermediate dioxanyl ester compounds of this invention are provided are conducted at an elevated temperature at which the desired S-m-dioxanyl acrylic ester is stable.
- an ester exchange catalyst such as an alkyl titanate, e.g., tetrabutyl titanate, or any other useful ester exchange catalyst such as an alkali metal alkoxide, or an alkali metal oxide, hydride, or hydroxide, or the like.
- the catalysts can be employed in general in amounts which are catalytic in ester exchange reactions.
- the S-m-dioX- anyl acrylic esters are provided by the following reaction:
- the desired acrylic dioxanyl esters are isolated from the ester exchange reaction mixture by conventional procedures.
- a relatively crude fraction of the desired dioxanyl esters can be obtained from the reaction mixture by fractional distillation.
- the crude products can be further purified as by extraction, precipitation, or distillation procedures of common knowledge to the art.
- it is advisable to destroy any residual catalyst activity prior to isolation treatment as by adding water to the reaction mixture and by extraction of the desired compound therefrom with an inert water immiscible solvent in which the desired ester is soluble, for example, benzene, toluene, and the like.
- S-hydroxyalkylene-m-dioxanyl alcohols can be provided following conventional condensation procedures illustrated by the following reaction:
- the symmetrical diols of this invention can be polymerized by following known methods for polymerizing acrylic type monomers. Polymerization can be conducted following bulk, solution, suspension, or emulsion polymerization techniques. Presently, it appears that solution polymerization results in a polymer having less cross linking and correspondingly greater solvent solubility than polymers produced by standard emulsion polymerizations. Conventional catalysts can be employed, and are ordinarily advisably used.
- Such referred to conventional polymerization catalysts include peroxide free-radical initiators such as benzoyl peroxide, tertiary butyl hydroperoxide, and tetriary butyl perbenzoate and the like; azotype free-radical catalysts such as alpha, alpha-azobis(isobutyronitrile), alpha, alpha'-azobis(ethyl isobutyrate), alpha, alpha azobis(isobutyramide), and the like; and persalts such as potassium persulfate and the like. It is desirable that the diol be free of ester exchange by-prodnets on polymerization, such as bis-esters, for example, Z-hydroxymethyl-Z-methyl-1,3-prpane diol bisacrylate or methacrylate.
- peroxide free-radical initiators such as benzoyl peroxide, tertiary butyl hydroperoxide, and tetriary butyl perbenzo
- the compounds of this invention can also be copolymerized with One or more ethylenically unsaturated monomers polymerizable therewith such as the alkyl esters of acrylic o-r methacrylic acid such as methyl methacrylate, ethyl acrylate, octyl acrylate, and benzyl acrylate, acrylamides such as methacrylamide; vinyl esters such as vinyl chloride and vinyl acetate; vinylidene chloride; acrylonitrile; allyl compounds such as diallyl adipate; vinyl aryl compounds such as styrene and divinyl benzene; and other unsaturated compounds like butadiene and maleic anhydride.
- ethylenically unsaturated monomers polymerizable therewith such as the alkyl esters of acrylic o-r methacrylic acid such as methyl methacrylate, ethyl acrylate, octyl acrylate, and benzy
- copolymers of this invention can be provided wherein a very small but efiective quantity of one or more of the above diols are incorporated.
- an eifective quantity of a symmetrical diol can be as small as about one percent by weight up to about ninety-nine percent by weight.
- the diols of this invention are contained in the polymers of the order of at least about two to about ninety percent by weight. It is to be understood that the exact concentration will vary depending upon the particular diol employed as well as the other ethylenically unsaturated monomer or monomers employed.
- copolymers can be made with a mixture of two or more of the novel diols with or without utilization of additional ethylenically unsaturated monomers.
- Certain agents and certain controls can be usefully employed in the polymerizations involving the acrylic ester. For example, control of temperatures and pressures can greatly contribute to the character of the end polymer products. It has been found that, when oxygen is excluded in for example a solution polymerization of the m-dioxanyl acrylic ester, the end polymers are relatively solvent soluble. However, if oxygen is present during the polymerization, apparently cross linking occurs and the end polymers are largely solvent insoluble. Certain agents acting as telogens can be employed. If emulsion polymerization is employed, emulsifying agents will be added such as fatty acid soaps, fatty acid esters of polyalkylene glycols, sulfated alcohols, or the like.
- the polymers provided hereby are useful in coating various objects, as adhesives and are useful in molding and casting operations.
- the'polymer can be ordinarily dissolved in a suitable solvent and laid down as a cast film.
- the end polymers can be foamed or they can be cross-linked as by application of heat or by the incorporation into the polymer mix a free radical providing catalyst such as peroxide catalyst.
- Example 1 A quantity of (2,2,S-trirnethyl-Sm-dioxanyl)methyl acrylate (5 g.) is added to 100 ml. of water and the solution pH is adjusted to pH 3 by the addition with stirring of dilute aqueous hydrochloric acid. The two phase reaction mixture is heated to 40-45 C. for 2 hrs. during which time the two phases become miscible. The reaction mixture is cooled, is neutralized by the addition of solid potassium carbonate, and is filtered. The filtered aqueous solution is extracted three times with chloroform. After drying over anhydrous sodium sulfate, the chloro form is removed leaving a residue of beta, beta-(bishydroxymethyl)propyl acrylate. The infrared spectrum of the product was in confirmation that the product is the propylene glycol desired.
- Example 2 The following additional 1,3-propane diols of this invention can be provided by following essentially the ring hydrolysis process of Example 1.
- the appropriate RR -substituted S-alkylene-m-dioxanyl arcylic esters are employed where in the dioxanyl portion has the following structure:
- the reaction mixture is heated to C. under an argon atmosphere and is stirred rapidly. After thirty minutes the remaining monomer emulsion is added dropwise over a onehour period. The reaction temperature is maintained for an additional approximately forty-five minutes, Whereupon the emulsion solidifies.
- the homopolymer product of beta, beta-(bishydroxymethyl)propyl methacrylate is relatively solvent insoluble.
- the homopolymer of beta, beta'(bishydroxymethyl) propyl arcylate disclosed in Example 1 can be homopolymerized following the above emulsion polymerization procedure.
- the monomers of Example 2 can be homopolymerized by this emulsion polymerization procedure.
- Example 4 A solution copolymerization of beta, beta-(bishydroxymethyl)propyl methacrylate, styrene, and n-butyl methacrylate is carried out as follows: twenty milliliters of a butanol-xylene solvent (1: l by volume) is refluxed under argon for one-half hour in a lO-ml., three-neck, round bottom flask equipper with a gas inlet, reflux condenser, syringe cap, and a magnetic stirring bar. Argon is also bubbled through a mixture of monomers, 57 g. of the methacrylate, 84 g. of styrene, and 51 g.
- Example 5 The procedure of Example 4 is repeated employing the following comonomer mixture: 26.5 g of beta, beta- (bishydroxymethyl)propyl methacrylate, 44 g. of styrene, and 20 g. of n-butyl rnethacrylate.
- 1,3- propane diols of Examples 12 can be homopolymerized and copolymerized with copolymerizable: ethylenically unsaturated monomers, e.g., acrylonitrile, butadiene, styrene, methyl acrylate, and the like.
- ethylenically unsaturated monomers e.g., acrylonitrile, butadiene, styrene, methyl acrylate, and the like.
- Example 6 The terpolymers provided by Examples 4 and 5 above are cured according to following procedure: Solutions of the terpolymers are thoroughly mixed with 30 percent by weight of a butylated melamine formaldehyde liquid resin product having a 50 percent solids content (the product is sold under the trademark Cymel 245-8 by American Cyanamid Company). The curing admixture is heated for one-half hour at 150 C. at a pressure of one atmosphere.
- the cured film product of the terpolymer of Example 4 has the following properties: a Sward hardness value of 68, a 60 gloss value of 98; and a film prepared from the cured terpolymer showed good resistance to butyl acetate, 5% sodium hydroxide, and a one-half percent aqueous solution of sodium lauryl sulfate at 73 C.
- the cured film product of the terpolymer of Example 5 (provided by the above procedure) showed a 60 gloss value of 100, showed a very slight crazing in eight hours on exposure to butyl acetate, showed good resistance to five percent aqueous sodium hydroxide, and showed a slight blistering within two hours to exposure to one-half percent aqueous solution of sodium lauryl sulfate at 73 C.
- Example 7 A homopolymer of beta, beta-(bishydroxymethyl) propyl methacrylate, is also readily obtained by mile hydrolysis of the homopolymer of (2,2,5-trimethyl-5- m-dioxanyl)methyl methacrylate.
- the homopolymer is obtained following conventional polymerization methods employing a bulk polymerization technique (as described in the above referred to copending application.
- the catalyst employed is 0.1 percent based on monomer weight of alpha, alpha-azobis(isobutyronitrile).
- preparation by hydrolysis of the homopolymer is carried on by adding one g. of the homopolymer to 17 ml. of an aqueous acetone solution consisting of 2 parts of water and 15 parts of acetone.
- the reaction mixture is acidified by the addition of p-toluene sulfonic acid to bring the pH to a pH of about 3.
- the temperature is maintained at 56 C. and the reaction is carried on for about one hour. Addition of more water is made from time to time to maintain the polymer in solution as the hydrolysis proceeds.
- the provided homopolymer of beta, beta-(bishydroxymethyl) propyl methacrylate is isolated by the following procedurezThe homopolymer is precipitated by the addi tion of either additional Water or acetone. The homopolymer is removed by filtration, and is dried in vacuo.
- a symmetrical, polymerizable 1,3-propane diol represented by the following formula:
- R is selected from the group consisting of hydrogen and lower alkyl radicals
- R is selected from the group consisting of lower alkyl radicals having one to four carbon atoms and hydrogen
- n represents an integer of from one to four, inclusive.
- H o o HoH CH (J( ,ocH 0H '3(3H Ha 11( 3H 12.
- a copolymer of a polymerizable compound of claim 1 and a copolymerizable ethylenically unsaturated monomer of the formula H C' C 24.
- a copolymer of a polymerizable compound of claim 2 and a copolymerizable ethylenically unsaturated monomer of the formula H C C 25.
- a copolymer of a polymerizable compound of claim 3 and a copolymerizable ethylenically unsaturated monomer of the formula H C C 26.
- a copolymer of a polymerizable compound of claim 4 and a copolymerizable ethylenically unsaturated monomer of the formula H C C 27.
- a copolymer of a polymerizable compound of claim 7 and a copolymerizable ethylenically unsaturated monomer of the formula H C C 30.
- a copolymer of a polymerizable compound of claim 8 and a copolymerizable ethylenically unsaturated monomer of the formula H C C 31.
- a copolymer of a polymerizable compound of claim 9 and a copolymerizable ethylenically unsaturated monomer of the formula H C C 32.
- a copolymer of a polymerizable compound of claim 10 and a polymerizable ethylenically unsaturated monomer of the formula H C C 33.
- a copolymer of a polymerizable compound of claim 11 and a copolymerizable ethylenically unsaturated monomer of the formula H C C 34.
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Description
United States Patent 3,210,327 SYMMETRICAL DIOL ALKYL ESTERS OF ACRYLIC ACIDS AND POLYMERS THEREOF Francis R. Galiano and Gerald J. Mantell, Kansas City, Mo., and David Rankin, Kansas City, Kans., assignors, by mesne assignments, to Gulf Oil Corporation, Pittsburgh, Pa., a corporation of Pennsylvania No Drawing. Filed May 23, 1962, Ser. No. 196,914
36 Claims. (Cl. 26080.5)
This invention relates to novel diol compounds. More particularly, it relates to novel symmetrical diols consisting of 1,3-prtpane diols having a 2-acrylic ester substitucut. The compounds are represented by the following formula:
H 0 El ie CH2 (]C0O(CH2)n CR1 wherein R is a hydrogen or a lower alkyl radical (preferably hydrogen or methyl), R is a lower alkyl radical having one to four carbon atoms or hydrogen, and n represents an integer from one to four, inclusive.
The symmetrical diols of this invention are generally relatively high boiling liquids. They are water-soluble and are in general soluble in polar solvents such as lower alkanols, e.g., methanol and ethanol, and in acetone, dioxane, ethyl acetate, and the like. The compounds of this invention can be homopolymerized or copolymerized with another polymerizable ethylenically unsaturated compound to form interpolymers. The polymers thereby provided have the interesting characteristic of being in most instances soluble in solvent combinations of water and water-miscible polar solvent such as acetone, ethanol, and the like. However, they on the other hand are not generally readily solubilized in Water alone.
Additionally, since the compounds are symmetrical diols as to both hydroxy functional groups, the compounds are readily reacted with a dicarboxylic acid agent to form polyesters. In polyester preparation, suitable elevated reaction temperatures will be used. Customary catalysts used by the skill of the art in polyester formation are desirably utilized. Suitable dicarboxylic acids for the ester formations include both aryl and aliphatic dicarboxylic acids illustrative of which are succinic, adipic, ophthalic, terephthalic, sebacic, 1,4-naphthalene-dicarboxylic, azelaic, glutaric, 3-ethylsebacic, and the like carboxylic acids. When appropriate, corresponding acid halides or anhydrides can be employed as the dicarboxylic acid agent. Relative proportions of the diols and dicarboxylic acids will be selected to insure polyester formation.
An important virtue of these polyesters is that they can be readily cured to form thermoset polymers conventionally by heating an admixture of the polymer and a catalytic amount of a free radical initiator such as a suitable peroxide, e.g., t-butyl perbenzoate. If desired, a quantity of a monomer can be added in preparation of the thermoset polymers to promote the linking of a double bonds of the acrylic substituents. Such monomers having unsaturation as styrene, triallyl isocyanurate, and the like can be employed for this purpose.
Furthermore, polyurethanes can be provided by reacting the diol with an organic diisocyanate such as toluene diisocyanate and hexamethylene diisocyanate, and the like.
The diols of this invention can readily be prepared as 3,210,327 Patented Oct. 5, 1965 ice by a mild aqueous acid hydrolysis of S-alkylene-m-dioxanyl acrylic esters such as disclosed in US. patent application filed concurrently herewith, Serial No. 196,916, by David Rankin et al. The following equation illustrates the hydrolysis procedure:
wherein R, R and n have the definitions set forth above. The carbon atom occupying position 2 in the dioxanyl ring can have any substituents to fulfill the valence requirements so long as the substituents do not prevent the necessary hydrolysis. The substituents are desirably both lower alkyl, suitably methyl, because of the relative ease by which such ketals hydrolyse to the desired compounds and the economy of such intermediates. However, other compounds having one or both substituents other than methyl can be employed. Illustratively speaking, the substituents can alternatively be ethyl, propyl, phenyl, or the like.
The hydrolysis is carried on by adding a suitable amount of the acrylic dioxanyl ester to an inert aqueous reaction solvent. Water is a satisfactory reaction solvent. The mixture is acidified'by adding a suitable acid. Mineral acids such as hydrochloric and sulfuric acid are satisfactory for this purpose. The pH of the reaction mixture is advisably lowered to about pH 5 or below, preferably to a pH in the range of about pH 2 to about pH 4. The reaction temperature can be room temperature but presently is preferred to be slightly above to provide a more eflicient and rapid hydrolysis, e.g., a temperature in the range of about 30 C. to about 60 C. is ordinarily satisfactory. A reaction time of from about one-half to about ten hours is ordinarily sufficient, depending on conditions and the intermediate employed. The reaction mixture is neutralized, is filtered, and the desired product is isolated as by extraction. Chloroform has been found to be a satisfactory extractant for aqueous reaction mixtures.
The ester exchange reactions by which the intermediate dioxanyl ester compounds of this invention are provided are conducted at an elevated temperature at which the desired S-m-dioxanyl acrylic ester is stable. Ordinarily it has been found useful to include in the reaction an ester exchange catalyst such as an alkyl titanate, e.g., tetrabutyl titanate, or any other useful ester exchange catalyst such as an alkali metal alkoxide, or an alkali metal oxide, hydride, or hydroxide, or the like. The catalysts can be employed in general in amounts which are catalytic in ester exchange reactions. In illustration, the S-m-dioX- anyl acrylic esters are provided by the following reaction:
The desired acrylic dioxanyl esters are isolated from the ester exchange reaction mixture by conventional procedures. For example, a relatively crude fraction of the desired dioxanyl esters can be obtained from the reaction mixture by fractional distillation. The crude products can be further purified as by extraction, precipitation, or distillation procedures of common knowledge to the art. In treating the reaction mixture, it is advisable to destroy any residual catalyst activity prior to isolation treatment as by adding water to the reaction mixture and by extraction of the desired compound therefrom with an inert water immiscible solvent in which the desired ester is soluble, for example, benzene, toluene, and the like.
The S-hydroxyalkylene-m-dioxanyl alcohols can be provided following conventional condensation procedures illustrated by the following reaction:
The symmetrical diols of this invention can be polymerized by following known methods for polymerizing acrylic type monomers. Polymerization can be conducted following bulk, solution, suspension, or emulsion polymerization techniques. Presently, it appears that solution polymerization results in a polymer having less cross linking and correspondingly greater solvent solubility than polymers produced by standard emulsion polymerizations. Conventional catalysts can be employed, and are ordinarily advisably used. Such referred to conventional polymerization catalysts include peroxide free-radical initiators such as benzoyl peroxide, tertiary butyl hydroperoxide, and tetriary butyl perbenzoate and the like; azotype free-radical catalysts such as alpha, alpha-azobis(isobutyronitrile), alpha, alpha'-azobis(ethyl isobutyrate), alpha, alpha azobis(isobutyramide), and the like; and persalts such as potassium persulfate and the like. It is desirable that the diol be free of ester exchange by-prodnets on polymerization, such as bis-esters, for example, Z-hydroxymethyl-Z-methyl-1,3-prpane diol bisacrylate or methacrylate.
The compounds of this invention can also be copolymerized with One or more ethylenically unsaturated monomers polymerizable therewith such as the alkyl esters of acrylic o-r methacrylic acid such as methyl methacrylate, ethyl acrylate, octyl acrylate, and benzyl acrylate, acrylamides such as methacrylamide; vinyl esters such as vinyl chloride and vinyl acetate; vinylidene chloride; acrylonitrile; allyl compounds such as diallyl adipate; vinyl aryl compounds such as styrene and divinyl benzene; and other unsaturated compounds like butadiene and maleic anhydride. It is to be understood that at times some of the above mentioned monomers will not polymerize in all concentrations or in all proportions with all of the 1,3- propane diols provided by this invention. However, copolymers of this invention can be provided wherein a very small but efiective quantity of one or more of the above diols are incorporated. For example, an eifective quantity of a symmetrical diol can be as small as about one percent by weight up to about ninety-nine percent by weight. Preferably, the diols of this invention are contained in the polymers of the order of at least about two to about ninety percent by weight. It is to be understood that the exact concentration will vary depending upon the particular diol employed as well as the other ethylenically unsaturated monomer or monomers employed.
It is to be further understood that copolymers can be made with a mixture of two or more of the novel diols with or without utilization of additional ethylenically unsaturated monomers.
Certain agents and certain controls can be usefully employed in the polymerizations involving the acrylic ester. For example, control of temperatures and pressures can greatly contribute to the character of the end polymer products. It has been found that, when oxygen is excluded in for example a solution polymerization of the m-dioxanyl acrylic ester, the end polymers are relatively solvent soluble. However, if oxygen is present during the polymerization, apparently cross linking occurs and the end polymers are largely solvent insoluble. Certain agents acting as telogens can be employed. If emulsion polymerization is employed, emulsifying agents will be added such as fatty acid soaps, fatty acid esters of polyalkylene glycols, sulfated alcohols, or the like.
The polymers provided hereby are useful in coating various objects, as adhesives and are useful in molding and casting operations. For example, the'polymer can be ordinarily dissolved in a suitable solvent and laid down as a cast film. The end polymers can be foamed or they can be cross-linked as by application of heat or by the incorporation into the polymer mix a free radical providing catalyst such as peroxide catalyst.
The following examples illustrate the provided invention but are not to be interpreted as being in limitation thereof except as defined by the appended claims.
Example 1 A quantity of (2,2,S-trirnethyl-Sm-dioxanyl)methyl acrylate (5 g.) is added to 100 ml. of water and the solution pH is adjusted to pH 3 by the addition with stirring of dilute aqueous hydrochloric acid. The two phase reaction mixture is heated to 40-45 C. for 2 hrs. during which time the two phases become miscible. The reaction mixture is cooled, is neutralized by the addition of solid potassium carbonate, and is filtered. The filtered aqueous solution is extracted three times with chloroform. After drying over anhydrous sodium sulfate, the chloro form is removed leaving a residue of beta, beta-(bishydroxymethyl)propyl acrylate. The infrared spectrum of the product was in confirmation that the product is the propylene glycol desired.
The above procedure is repeated employing (2,2,5- trimethyl-S-m-dioxanyl)methyl methacrylate as the starting compound to provide the corresponding beta, beta- (bishydroxymethyl)propyl methacrylate.
Example 2 The following additional 1,3-propane diols of this invention can be provided by following essentially the ring hydrolysis process of Example 1. The appropriate RR -substituted S-alkylene-m-dioxanyl arcylic esters are employed where in the dioxanyl portion has the following structure:
GE -O CH The required acrylic dioxanyl intermediate is prepared and also described in the cited copending application.
H O I i l g moo H 0 nl mo-olIl The polymerization of beta, beta-(bishydroxymethyl) propyl methacrylate is carried out in an emulsion system. Sodium lauryl sulfate (0.2 g.) is dissolved in 7 ml. of distilled Water and 6.4 g. of the methacrylate is added. This mixture is placed in an addition funnel and is shaken vigorously to dissolve the monomer. Potassium persulfate (32 g. in 4 ml. of Water) and the monomer are added to a 100-ml., round-bottom flask equipped with a paddle stirrer, a reflux condenser and a gas inlet. The reaction mixture is heated to C. under an argon atmosphere and is stirred rapidly. After thirty minutes the remaining monomer emulsion is added dropwise over a onehour period. The reaction temperature is maintained for an additional approximately forty-five minutes, Whereupon the emulsion solidifies. The homopolymer product of beta, beta-(bishydroxymethyl)propyl methacrylate is relatively solvent insoluble.
The homopolymer of beta, beta'(bishydroxymethyl) propyl arcylate disclosed in Example 1 can be homopolymerized following the above emulsion polymerization procedure. Likewise, the monomers of Example 2 can be homopolymerized by this emulsion polymerization procedure.
Example 4 A solution copolymerization of beta, beta-(bishydroxymethyl)propyl methacrylate, styrene, and n-butyl methacrylate is carried out as follows: twenty milliliters of a butanol-xylene solvent (1: l by volume) is refluxed under argon for one-half hour in a lO-ml., three-neck, round bottom flask equipper with a gas inlet, reflux condenser, syringe cap, and a magnetic stirring bar. Argon is also bubbled through a mixture of monomers, 57 g. of the methacrylate, 84 g. of styrene, and 51 g. of n-butyl methacrylate for one-half hour at room temperature. A quantity of 0.4 g. of alpha, alpha'-azobis(isobutyronitrile) is then dissolved in 19.2 g. of the above monomer mixture. The monomer catalyst mixture is added dropwise with a syringe to the heated solvent mixture over a period of one-half hour. The reaction mixture is then heated for six hours at reflux temperature. After cooling, the reaction mixture is filtered to remove a slight amount of solid material. The filtrate contains the terpolymer of beta, beta-(bishydroxymethyDpropyl methacrylate, styrene, and n-butyl methacrylate.
Example 5 The procedure of Example 4 is repeated employing the following comonomer mixture: 26.5 g of beta, beta- (bishydroxymethyl)propyl methacrylate, 44 g. of styrene, and 20 g. of n-butyl rnethacrylate.
Additionally, following the polymerization procedures set out in Examples 3 and 4 above, the remaining 1,3- propane diols of Examples 12 can be homopolymerized and copolymerized with copolymerizable: ethylenically unsaturated monomers, e.g., acrylonitrile, butadiene, styrene, methyl acrylate, and the like.
Example 6 The terpolymers provided by Examples 4 and 5 above are cured according to following procedure: Solutions of the terpolymers are thoroughly mixed with 30 percent by weight of a butylated melamine formaldehyde liquid resin product having a 50 percent solids content (the product is sold under the trademark Cymel 245-8 by American Cyanamid Company). The curing admixture is heated for one-half hour at 150 C. at a pressure of one atmosphere.
The cured film product of the terpolymer of Example 4 has the following properties: a Sward hardness value of 68, a 60 gloss value of 98; and a film prepared from the cured terpolymer showed good resistance to butyl acetate, 5% sodium hydroxide, and a one-half percent aqueous solution of sodium lauryl sulfate at 73 C.
The cured film product of the terpolymer of Example 5 (provided by the above procedure) showed a 60 gloss value of 100, showed a very slight crazing in eight hours on exposure to butyl acetate, showed good resistance to five percent aqueous sodium hydroxide, and showed a slight blistering within two hours to exposure to one-half percent aqueous solution of sodium lauryl sulfate at 73 C.
Example 7 A homopolymer of beta, beta-(bishydroxymethyl) propyl methacrylate, is also readily obtained by mile hydrolysis of the homopolymer of (2,2,5-trimethyl-5- m-dioxanyl)methyl methacrylate. The homopolymer is obtained following conventional polymerization methods employing a bulk polymerization technique (as described in the above referred to copending application. The catalyst employed is 0.1 percent based on monomer weight of alpha, alpha-azobis(isobutyronitrile). The
preparation by hydrolysis of the homopolymer is carried on by adding one g. of the homopolymer to 17 ml. of an aqueous acetone solution consisting of 2 parts of water and 15 parts of acetone. The reaction mixture is acidified by the addition of p-toluene sulfonic acid to bring the pH to a pH of about 3. The temperature is maintained at 56 C. and the reaction is carried on for about one hour. Addition of more water is made from time to time to maintain the polymer in solution as the hydrolysis proceeds.
The provided homopolymer of beta, beta-(bishydroxymethyl) propyl methacrylate is isolated by the following procedurezThe homopolymer is precipitated by the addi tion of either additional Water or acetone. The homopolymer is removed by filtration, and is dried in vacuo.
The above procedure can be repeated to provide homopolymers and certain copolymers of the remaining monomers of Examples 1 and 2 wherein polymers of the corresponding S-alkylene-m-dioxanyl acrylic ester are employed as starting polymers. The 2,2-dimethyl-5-m-dioxanyl rings are converted then in the procedure to the required 1,3-propane diol structure.
What is claimed is:
1. A symmetrical, polymerizable 1,3-propane diol represented by the following formula:
wherein R is selected from the group consisting of hydrogen and lower alkyl radicals, R is selected from the group consisting of lower alkyl radicals having one to four carbon atoms and hydrogen, and n represents an integer of from one to four, inclusive.
. A polymerizable compound of the formula:
4. A polymerizable compound of the formula:
. A polymerizable compound of the formula:
I (I) HCH CH3 Ha /H 9 6. A polymerizable compound of the formula:
H o H4111 CHFOHH/O-OHg-CgH HCH 7. A polymerizable compound of the formula:
H 0 0 aa CH =of :-o-oH 30 H Ha H H 8. A polymerizable compound of the formula:
H o H( )H CH =CH (l-0(JII OH EH HCH I H 9. A polymerizable compound of the formula:
H o HdH (3H =C-il0cH -OH -11 10. A polymerizable compound of the formula:
H o 0 H(JH CH CH( 3OCHz-CH2CHa H H t) H 11. A polymerizable compound of the formula:
H o o HoH CH =(J( ,ocH 0H '3(3H Ha 11( 3H 12. A homopolymer of a polymerizable compound of claim 1.
13. A homopolymer of the polymerizable compound of claim 2.
14. A homopolymer of the polymerizable compound of claim 3.
15. A homopolymer of the polymerizable compound of claim 4.
16. A homopolymer of the polymerizable compound of claim 5.
17. A homopolymer of the polymerizable compound of claim 6.
18. A homopolymer of the polymerizable compound of claim 7.
19. A homopolymer of the polymerizable compound of claim 8.
20. A homopolymer of the polymerizable compound of claim 9.
21. A homopolymer of the polymerizable compound of claim 10.
22. A homopolymer of the polymerizable compound of claim 11.
23. A copolymer of a polymerizable compound of claim 1 and a copolymerizable ethylenically unsaturated monomer of the formula H C'=C 24. A copolymer of a polymerizable compound of claim 2 and a copolymerizable ethylenically unsaturated monomer of the formula H C=C 25. A copolymer of a polymerizable compound of claim 3 and a copolymerizable ethylenically unsaturated monomer of the formula H C=C 26. A copolymer of a polymerizable compound of claim 4 and a copolymerizable ethylenically unsaturated monomer of the formula H C=C 27. A copolymer of a polymerizable compound of claim 5 and a copolymerizable ethylenically unsaturated monomer of the formula H @C 28. A copolymer of a polymerizable compound of claim 6 and a copolymerizable ethylenically unsaturated monomer of the formula H C' -C 29. A copolymer of a polymerizable compound of claim 7 and a copolymerizable ethylenically unsaturated monomer of the formula H C=C 30. A copolymer of a polymerizable compound of claim 8 and a copolymerizable ethylenically unsaturated monomer of the formula H C=C 31. A copolymer of a polymerizable compound of claim 9 and a copolymerizable ethylenically unsaturated monomer of the formula H C=C 32. A copolymer of a polymerizable compound of claim 10 and a polymerizable ethylenically unsaturated monomer of the formula H C=C 33. A copolymer of a polymerizable compound of claim 11 and a copolymerizable ethylenically unsaturated monomer of the formula H C=C 34. A process of providing a polymerizable compound of claim 1 by acid hydrolysing a suitable S-alkylene-mdioxanyl acrylic ester having the formula:
References Cited by the Examiner UNITED STATES PATENTS 6/54 Fegley et a1. 26086.1 2/60 Pattison 260-88.3
FOREIGN PATENTS 852,384 10/60 Great Britain.
JOSEPH L. SCHOFER, Primary Examiner.
I. R. LIBERMAN, Examiner.
Claims (2)
1. A SYMMETRICAL, POLYMERIZABLE 1,3-PROPANE DIOL REPRESENTED BY THE FOLLOWING FORMULA:
23. A COPOLYMER OF A POLYMERIZABLE COMPOUND OF CLAIM 1 AND A COPOLYMERIZABLE ETHYLENICALLY UNSATURATED MONOMER OF THE FORMULA H2C=C<.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US196914A US3210327A (en) | 1962-05-23 | 1962-05-23 | Symmetrical diol alkyl esters of acrylic acids and polymers thereof |
FR935755A FR1366079A (en) | 1962-05-23 | 1963-05-22 | New glycol compounds and processes for their preparation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US196914A US3210327A (en) | 1962-05-23 | 1962-05-23 | Symmetrical diol alkyl esters of acrylic acids and polymers thereof |
Publications (1)
Publication Number | Publication Date |
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US3210327A true US3210327A (en) | 1965-10-05 |
Family
ID=22727263
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US196914A Expired - Lifetime US3210327A (en) | 1962-05-23 | 1962-05-23 | Symmetrical diol alkyl esters of acrylic acids and polymers thereof |
Country Status (1)
Country | Link |
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US (1) | US3210327A (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4031053A (en) * | 1976-02-05 | 1977-06-21 | Celanese Corporation | Protective colloids from alcoholysis products of polyalcohols and polyacrylate esters |
US4508594A (en) * | 1984-06-28 | 1985-04-02 | Nalco Chemical Company | Polyaldehyde/polyacetal compositions |
US4529786A (en) * | 1981-03-30 | 1985-07-16 | Celanese Corporation | Acrylate and methacrylate monoesters of pentaerythritol and pentaerythritol orthoesters and polymers and copolymers derived therefrom |
US4605718A (en) * | 1984-06-28 | 1986-08-12 | Nalco Chemical Company | Polyaldehyde/polyacetal compositions |
EP0309249A2 (en) * | 1987-09-22 | 1989-03-29 | Minnesota Mining And Manufacturing Company | Acryloyloxy and methacryloyloxy group-containing condensation polymers |
US4921930A (en) * | 1987-09-22 | 1990-05-01 | Minnesota Mining And Manufacturing Company | Acryloyloxy and methacryloyloxy group-containing condensation polymers |
DE10118232A1 (en) * | 2001-04-11 | 2002-10-24 | Roehm Gmbh | 1,3 Diol compounds, useful as comonomers in dental applications, are prepared by hydrolysis of the corresponding ketal in the presence of an acid ion exchange medium in a polar solvent and water. |
WO2015000123A1 (en) * | 2013-07-02 | 2015-01-08 | Dic Corporation | Method for manufacturing (meth)acryloyl group-containing polyol compound, (meth)acryloyl group-containing polyol compound, and urethane (meth)acrylate |
JPWO2018230322A1 (en) * | 2017-06-12 | 2019-11-14 | Dic株式会社 | Polymerizable compound and liquid crystal composition |
US11739270B2 (en) | 2018-03-01 | 2023-08-29 | Dic Corporation | Polymerizable compound as well as liquid crystal composition and liquid crystal display device each including polymerizable compound |
US11760934B2 (en) | 2017-11-17 | 2023-09-19 | Dic Corporation | Polymerizable compound, and liquid crystal composition and liquid crystal display element in which the compound is used |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2680735A (en) * | 1952-07-09 | 1954-06-08 | Rohm & Haas | Resinous esters of acrylic acid and methacrylic acid |
US2924607A (en) * | 1957-10-18 | 1960-02-09 | Du Pont | Preparation of oxetanes |
GB852384A (en) * | 1957-07-16 | 1960-10-26 | Rohm & Haas | Process for preparing dihydroxy alkyl acrylates and methacrylates |
-
1962
- 1962-05-23 US US196914A patent/US3210327A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2680735A (en) * | 1952-07-09 | 1954-06-08 | Rohm & Haas | Resinous esters of acrylic acid and methacrylic acid |
GB852384A (en) * | 1957-07-16 | 1960-10-26 | Rohm & Haas | Process for preparing dihydroxy alkyl acrylates and methacrylates |
US2924607A (en) * | 1957-10-18 | 1960-02-09 | Du Pont | Preparation of oxetanes |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4031053A (en) * | 1976-02-05 | 1977-06-21 | Celanese Corporation | Protective colloids from alcoholysis products of polyalcohols and polyacrylate esters |
US4529786A (en) * | 1981-03-30 | 1985-07-16 | Celanese Corporation | Acrylate and methacrylate monoesters of pentaerythritol and pentaerythritol orthoesters and polymers and copolymers derived therefrom |
US4508594A (en) * | 1984-06-28 | 1985-04-02 | Nalco Chemical Company | Polyaldehyde/polyacetal compositions |
US4605718A (en) * | 1984-06-28 | 1986-08-12 | Nalco Chemical Company | Polyaldehyde/polyacetal compositions |
EP0309249A2 (en) * | 1987-09-22 | 1989-03-29 | Minnesota Mining And Manufacturing Company | Acryloyloxy and methacryloyloxy group-containing condensation polymers |
US4910281A (en) * | 1987-09-22 | 1990-03-20 | Minnesota Mining And Manufacturing Company | Acryloyloxy and methacryloyloxy group-containing condensation polymers |
EP0309249A3 (en) * | 1987-09-22 | 1990-04-18 | Minnesota Mining And Manufacturing Company | Acryloyloxy and methacryloyloxy group-containing condensation polymers |
US4921930A (en) * | 1987-09-22 | 1990-05-01 | Minnesota Mining And Manufacturing Company | Acryloyloxy and methacryloyloxy group-containing condensation polymers |
DE10118232A1 (en) * | 2001-04-11 | 2002-10-24 | Roehm Gmbh | 1,3 Diol compounds, useful as comonomers in dental applications, are prepared by hydrolysis of the corresponding ketal in the presence of an acid ion exchange medium in a polar solvent and water. |
WO2015000123A1 (en) * | 2013-07-02 | 2015-01-08 | Dic Corporation | Method for manufacturing (meth)acryloyl group-containing polyol compound, (meth)acryloyl group-containing polyol compound, and urethane (meth)acrylate |
JP2015526426A (en) * | 2013-07-02 | 2015-09-10 | Dic株式会社 | Method for producing (meth) acryloyl group-containing polyol compound, (meth) acryloyl group-containing polyol compound, and urethane (meth) acrylate |
CN105408300A (en) * | 2013-07-02 | 2016-03-16 | Dic株式会社 | Method for manufacturing (meth)acryloyl group-containing polyol compound, (meth)acryloyl group-containing polyol compound, and urethane (meth)acrylate |
JPWO2018230322A1 (en) * | 2017-06-12 | 2019-11-14 | Dic株式会社 | Polymerizable compound and liquid crystal composition |
US11174217B2 (en) | 2017-06-12 | 2021-11-16 | Dic Corporation | Polymerizable compound and liquid crystal composition |
US11760934B2 (en) | 2017-11-17 | 2023-09-19 | Dic Corporation | Polymerizable compound, and liquid crystal composition and liquid crystal display element in which the compound is used |
US11739270B2 (en) | 2018-03-01 | 2023-08-29 | Dic Corporation | Polymerizable compound as well as liquid crystal composition and liquid crystal display device each including polymerizable compound |
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